Multilayer ceramics from silicate esters

ABSTRACT

This invention relates to materials produced by diluting in a solvent a preceramic mixture of a partially hydrolyzed silicate ester which is applied to a substrate and ceramified by heating. One or more ceramic coatings containing silicon carbon, silicon nitrogen, or silicon carbon nitrogen can be applied over the ceramified SiO 2  coating. A CVD or PECVD top coating can be applied for further protection. The invention is particularly useful for coating electronic devices.

BACKGROUND OF THE INVENTION

Electronic devices, to be serviceable under a wide variety ofenvironmental conditions, must be able to withstand moisture, heat, andabrasion resistance, among other stresses. A significant amount of workhas been reported directed toward the preparation of coatings forelectronic devices which can increase the reliability of the devices.None of the conventional coatings available today, including ceramic andmetal packaging, can perform well enough by itself to protect anelectronic device against all environmental stresses.

A common cause of failure of electronic devices is microcracks or voidsin the surface passivation of the semiconductor chip allowing theintroduction of impurities. Thus a need exists for a method which willovercome the formation of microcracks, voids or pinholes in inorganiccoatings of electronic devices.

Passivating coatings on electronic devices can provide barriers againstionic impurities, such as chloride ion (Cl-) and sodium ion (Na+), whichcan enter an electronic device and disrupt the transmission ofelectronic signals. The passivating coating can also be applied toelectronic devices to provide some protection against moisture andvolatile organic chemicals.

Amorphous silicon (hereinafter a-Si) films have been the subject ofintense research for various applications in electronic industries,however, the use of a-Si films for environmental or hermetic protectionof electronic devices is unknown. A number of possible processes havebeen previously disclosed for forming a-Si films. For instance, forproducing films of amorphous silicon, the following deposition processeshave been used: chemical vapor deposition (CVD), plasma enhanced CVD(PECVD), reactive sputtering, ion plating and photo-CVD, etc. Generally,the plasma enhanced CVD process is industrialized and widely used fordepositing a-Si films.

Known to those skilled in the art is the utility of substrateplanarization as an interlayer within the body of an electronic deviceand between the metallization layers. Gupta and Chin (MicroelectronicsProcessing, Chapter 22, "Characteristics of Spin-On Glass Films as aPlanarizing Dielectric", pp349-65, American Chemical Society, 1986) haveshown multilevel interconnect systems with isolation of metallizationlevels by conventional interlevel dielectric insulator layers of dopedor undoped SiO₂ glass films. However, CVD dielectric films provide onlyat best a conformal coverage of substrate features which is notconducive to continuous and uniform step coverage by an overlyingmetallization layer. The poor step coverage results in discontinuous andthin spots in the conductor lines causing degradation of metallizationyields as well as device reliability problems. Spin-on glass films havebeen utilized to provide interlayer isolation between the metallizationlayers, the top layer of which is later patterned by lithographictechniques. Topcoat planarization on the surface of an electronic deviceas opposed to planarizing interlevel dielectric layers, however, isunknown.

Under the teachings of the prior art, a single material most often willnot suffice to meet the ever increasing demands of specialty coatingapplications, such as those found in the electronics industry. Severalcoating properties such as microhardness, moisture resistance, ionbarrier, adhesion, ductility, tensile strength, thermal expansioncoefficients, etc., need to be provided by successive layers ofdifferent coatings.

Silicon and nitrogen-containing preceramic polymers, such as silazaneshave been disclosed in various patents, including U.S. Pat. No.4,404,153, issued Sept. 13, 1983 to Gaul, wherein there is disclosed aprocess for preparing R'₃ SiNH-- containing silazane polymers bycontacting and reacting chlorine-containing disilanes with (R'₃ Si)₂ NHwhere R' is vinyl, hydrogen, an alkyl radical of 1 to 3 carbon atoms orthe phenyl group. Gaul also teaches therein the use of the preceramicsilazane polymers to produce silicon-carbon-nitrogen-containing ceramicmaterials.

Gaul in U.S. Pat. No. 4,312,970, issued Jan. 26, 1982, obtained ceramicmaterials by the pyrolysis of preceramic silazane polymers, whichpolymers were prepared by reacting organochlorosilanes and disilazanes.

Gaul in U.S. Pat. No. 4,340,619, issued July 20, 1982, obtained ceramicmaterials by the pyrolysis of preceramic silazane polymers, whichpolymers were prepared by reacting chlorine-containing disilanes anddisilazanes.

Cannady in U.S. Pat. No. 4,540,803, issued Sept. 10, 1985, obtainedceramic materials by the pyrolysis of preceramic silazane polymers,which polymers were prepared by reacting trichlorosilane anddisilazanes.

The instant invention relates to the enhancement of the protection ofelectronic devices by the low temperature formation of thin multilayerceramic or ceramic-like coatings on the surface of the device. What hasbeen discovered is a method of forming one or more silicon-andnitrogen-containing ceramic or ceramic-like coatings for the protectionof electronic devices.

SUMMARY OF THE INVENTION

The instant invention relates to a process for the low temperatureformation of multilayer and monolayer coatings for the protection ofelectronic devices. The monolayer coating for the protection ofelectronic devices consists of ceramified silicon dioxide layerdeposited from a solution of preceramic silicate polymer. The dual-layercoatings of the present invention consist of (1) a coating prepared bydepositing on an electronic device a solvent solution of a materialcontaining silicon and oxygen, wherein upon heat treatment the materialceramifies to form a SiO₂ -containing material, and (2) a top coating ofsilicon-containing material, or silicon nitrogen-containing material, orsilicon carbon-containing material, or silicon carbonnitrogen-containing material.

The first layer applied over the electronic device is a SiO₂ -containingplanarizing and passivating coating that is applied by known coatingtechniques, including flow coating, spin coating, dip coating and spraycoating of an electronic device. The second layer is a hermetic-typebarrier coating of silicon-containing material derived from the CVD,PECVD or metal assisted CVD of halosilanes, halopolysilanes,halodisilanes, silanes or mixtures thereof with or without alkanes. Themetal-assisted CVD process is claimed in the parallel U.S. patentapplication, Ser. No. 835,029, filed Feb. 28, 1986 in the name ofSudarsanan Varaprath and entitled "Silicon-containing Coatings and aMethod for Their Preparation".

The instant invention also relates to the formation of a three layercoating system for the protection of electronic devices wherein thefirst layer is an SiO₂ -containing planarizing coating obtained from asolvent solution of a material containing silicon and oxygen, wherein,upon heat treatment, the material ceramifies to form an SiO₂ -containingmaterial. Such materials can include, but are not limited to, organicorthosilicates, Si(OR)₄, or condensed esters of the type (RO)₃SiOSi(OR)₃, and any other source of SiOR such that upon hydrolysis andsubsequent pyrolysis a material of essentially SiO₂ is produced. Thus,materials containing carbon, such as SiOC-containing materials, can beincluded in this group if the carbon-containing group is hydrolyzableunder the thermal conditions so as to volatilize out leaving essentiallySiO₂. The second layer, used for passivation, is a ceramic orceramic-like coating obtained by the ceramification of a preceramicSiN-containing polymer coating, or is a silicon nitrogen-containing,silicon carbon nitrogen-containing, or silicon carbon-containing layerdeposited by thermal, UV, CVD, plasma enhanced CVD, or laser techniques.The third layer in the three layer coatings of the present invention isa top coating of (a) silicon-containing material applied by CVD, plasmaenhanced CVD, or metal assisted CVD of a silane, halosilane,halodisilane, halopolysilane, or mixtures thereof, or (b) siliconcarbon-containing material, applied by CVD or plasma enhanced CVD of asilane, alkylsilane, halosilane, halodisilane, halopolysilane, ormixtures thereof, and an alkane or alkylsilane, or (c) siliconnitrogen-containing material applied by CVD or plasma enhanced CVD of asilane, halosilane, halodisilane, halopolysilane, or mixtures thereof,and ammonia, or (d) silicon carbon nitrogen-containing material appliedby CVD or plasma enhanced CVD of hexamethyldisilazane or a mixture ofsilanes, alkylsilanes, alkanes and ammonia.

DETAILED DESCRIPTION OF THE INVENTION

The instant invention relates to the discovery that silicon dioxide(SiO₂ -containing) ceramic or ceramic-like coatings derived from theceramification of a silicate ester solution can be applied ontoelectronic devices and integrated circuits to provide protection of thedevices or circuits from the environment.

The instant invention further relates to the discovery that thesesilicon dioxide (SiO₂ -containing) ceramic or ceramic-like coatings canbe coated with various silicon, carbon and nitrogen-containing materialsfor the protection of electronic devices as well as other integratedcircuits.

In the instant invention, by "ceramic-like" is meant those pyrolyzedmaterials which are not fully free of residual carbon and/or hydrogenbut which are otherwise ceramic-like in character. By "hydrolyzedsilicate ester" in the instant invention is meant any SiO₂ -containingmaterial, as described above, which has been hydrolyzed or partiallyhydrolyzed by treatment with, for example, aqueous, basic, or acidicconditions. By "electronic device" in the instant invention is meantdevices including, but not limited to, electronic devices, silicon baseddevices, gallium arsenide devices, focal plane arrays, opto-electronicdevices, photovoltaic cells, optical devices, and the like. The coatingsof the instant invention are also useful as dielectric layers, dopeddielectric layers to produce transistor-like devices, pigment loadedbinder systems containing silicon to produce capacitors andcapacitor-like devices, multilayer devices, 3-D devices,silicon-on-insulator (SOI) devices, super lattice devices and the like.

The instant invention also relates to a process for the formation ofsilicon-containing top coatings for ceramic or ceramic-like coatingelectronic devices whereby the topcoat is prepared by plasma enhancedCVD, metal assisted CVD (MACVD) techniques, or other CVD techniques.

The instant invention also relates to a process for forming on thesubstrate a ceramic or ceramic-like SiO₂ coating which process comprises(A) coating an electronic device with a planarized coating by means ofdiluting a hydrolyzed or partially hydrolyzed silicate ester to lowsolids with a solvent and applying the diluted hydrolyzed or partiallyhydrolyzed silicate ester solution to an electronic device; (B) dryingthe diluted hydrolyzed or partially hydrolyzed silicate ester solutionso as to evaporate the solvent and thereby deposit a preceramic coatingon the electronic device; (C) ceramifying the hydrolyzed or partiallyhydrolyzed silicate ester to silicon dioxide by heating the coatingdevice to a temperature between 20 and 1000 degrees Centigrade toproduce the ceramic or ceramic-like planarizing SiO₂ coating on thedevice.

In addition, the instant invention relates to a process for forming on asubstrate a multilayer, ceramic or ceramic-like, coating which processcomprises (A) coating an electronic device with a coating by means ofdiluting a hydrolyzed or partially hydrolyzed silicate ester preceramicmaterial with a solvent, coating an electronic device with said dilutedhydrolyzed or partially hydrolyzed silicate ester preceramic materialsolution, drying the diluted hydrolyzed or partially hydrolyzed silicateester preceramic material solution so as to evaporate the solvent andthereby deposit a hydrolyzed or partially hydrolyzed silicate esterpreceramic coating on the electronic device, ceramifying the hydrolyzedor partially hydrolyzed silicate ester preceramic coating to silicondioxide by heating the coated device to a temperature between 200 and1000 degrees Centigrade to produce the ceramic or ceramic-like SiO₂coating and (B) applying to the ceramic or ceramic-like SiO₂ coateddevice a silicon-containing coating by means of decomposing in areaction chamber a silane, halosilane, halodisilane, halopolysilane, ormixture thereof in the vapor phase, at a temperature between 200 and 600degrees Centigrade, in the presence of the ceramic or ceramic-likecoated device, whereby an electronic device containing a multilayer,ceramic or ceramic-like, coating thereon is obtained. The process forapplying the planarizing or passivating coatings on the electronicdevice can be, but is not limited to, flow coating, spin coating, sprayor dip coating techniques.

The instant invention further relates to a process for forming on asubstrate a multilayer, ceramic or ceramic-like, coating which processcomprises (A) coating an electronic device with a coating by means ofdiluting a hydrolyzed or partially hydrolyzed silicate ester preceramicmaterial with a solvent, coating an electronic device with said dilutedhydrolyzed or partially hydrolyzed silicate ester preceramic materialsolution, drying the diluted hydrolyzed or partially hydrolyzed silicateester preceramic material solution so as to evaporate the solvent andthereby deposit a hydrolyzed or partially hydrolyzed silicate esterpreceramic material coating on the electronic device, ceramifying thehydrolyzed or partially hydrolyzed silicate ester preceramic materialcoating to silicon dioxide by heating the coated device to a temperaturebetween 200 and 1000 degrees Centigrade to produce the ceramic orceramic-like coating, and (B) applying to the ceramic or ceramic-likecoated device a silicon nitrogen-containing coating by means of applyingto the ceramic or ceramic-like coated device a passivating coatingcomprising a silicon nitrogen-containing material produced by means ofdiluting in a solvent a preceramic silicon nitrogen-containing polymer,coating the ceramic or ceramic-like coated device with the dilutedpreceramic silicon nitrogen-containing polymer solution, drying thediluted preceramic silicon nitrogen-containing polymer solution as so toevaporate the solvent and thereby deposit a preceramic siliconnitrogen-containing coating on the ceramic or ceramic-like coatedelectronic device, and heating the coated device to a temperature of 200to 1000 degrees Centigrade in an inert or ammonia-containing atmosphereto produce the ceramic or ceramic-like silicon nitrogen-containingcoating on the electronic device.

The instant invention also relates to a process for forming on asubstrate a multilayer, ceramic or ceramic-like, coating which processcomprises (A) coating an electronic device with a coating by means ofdiluting a hydrolyzed or partially hydrolyzed silicate ester preceramicmaterial with a solvent, coating an electronic device with said dilutedhydrolyzed or partially hydrolyzed silicate ester preceramic materialsolution, drying the diluted hydrolyzed or partially hydrolyzed silicateester preceramic material solution so as to evaporate the solvent andthereby deposit a hydrolyzed or partially hydrolyzed silicate esterpreceramic material coating on the electronic device, ceramifying thehydrolyzed or partially hydrolyzed silicate ester preceramic materialcoating to silicon dioxide by heating the coated device to a temperaturebetween 200 and 1000 degrees Centigrade to produce the ceramic orceramic-like coating, and (B) applying to the ceramic or ceramic-likecoated device a silicon carbon-containing coating by means ofdecomposing in a reaction chamber a silane, alkylsilane, halosilane,halodisilane, halopolysilane, or mixture thereof, and a materialselected from the group consisting of alkanes of one to six carbonatoms, alkylsilanes, and alkylhalosilanes, in the vapor phase, at atemperature between 200 and 1000 degrees Centigrade, in the presence ofthe ceramic or ceramic-like coated device, whereby an electronic devicecontaining a multilayer, ceramic or ceramic-like, coating thereon isobtained.

The instant invention further relates to a process for forming on asubstrate a multilayer, ceramic or ceramic-like, coating which processcomprises (A) coating an electronic device with a ceramic orceramic-like coating by means of diluting a hydrolyzed or partiallyhydrolyzed silicate ester preceramic material with a solvent, coating anelectronic device with said diluted hydrolyzed or partially hydrolyzedsilicate ester preceramic material solution, drying the dilutedhydrolyzed or partially hydrolyzed silicate ester preceramic materialsolution so as to evaporate the solvent and thereby deposit a hydrolyzedor partially hydrolyzed silicate ester preceramic material coating onthe electronic device, ceramifying the hydrolyzed or partiallyhydrolyzed silicate ester preceramic material coating to silicon dioxideby heating the coated device to a temperature between 200 and 1000degrees Centigrade to produce the ceramic or ceramic-like coating, and(B) applying to the ceramic or ceramic-like coated device a passivatingcoating which comprises a silicon nitrogen-containing material by meansof diluting with a solvent a preceramic silicon nitrogen-containingpolymer, coating the ceramic or cerammic-like coated device with thepreceramic silicon nitrogen-containing polymer solution, drying thepreceramic silicon nitrogen-containing polymer solution so as toevaporate the solvent and thereby deposit a preceramic siliconnitrogen-containing coating on the ceramic or ceramic-like coatedelectronic device, heating the coated device to a temperature of 200 to1000 degrees Centigrade in an inert or ammonia-containing atmosphere toproduce the ceramic or ceramic-like silicon nitrogen-containing coating,and (C) applying to the ceramic or ceramic-like coated device asilicon-containing coating by means of decomposing in a reaction chambera silane, halosilane, halodisilane or halopolysilane or mixture thereofin the vapor phase, at a temperature between 200 and 1000 degreesCentigrade, in the presence of the ceramic or ceramic-like coateddevice, whereby an electronic device containing a multilayer, ceramic orceramic-like, coating thereon is obtained.

The invention also relates to a process for forming on a substrate amultilayer, ceramic or ceramic-like, coating which process comprises (A)coating an electronic device with a coating by means of diluting ahydrolyzed or partially hydrolyzed silicate ester preceramic materialwith a solvent, coating an electronic device with said dilutedhydrolyzed or partially hydrolyzed silicate ester preceramic materialsolution, drying the diluted hydrolyzed or partially hydrolyzed silicateester preceramic material solution so as to evaporate the solvent andthereby deposit a hydrolyzed or partially hydrolyzed silicate esterpreceramic material coating on the electronic device, ceramifying thehydrolyzed or partially hydrolyzed silicate ester preceramic materialcoating to silicon dioxide by heating the coated device to a temperaturebetween 200 and 1000 degrees Centigrade to produce the ceramic orceramic-like coating, and (B) applying to the ceramic or ceramic-likecoated device a passivating coating which comprises a siliconnitrogen-containing material by means of diluting with a solvent apreceramic silicon nitrogen-containing polymer, coating the ceramic orceramic-like coated device with the diluted preceramic siliconnitrogen-containing polymer solution, dyring the diluted preceramicsilicon nitrogen-containing polymer solution so as to evaporate thesolvent and thereby deposit a preceramic silicon nitrogen-containingcoating on the ceramic or ceramic-like coated electronic device, heatingthe coated device to a temperaure between 200 and 1000 degreesCentigrade in an inert or ammonia-containing atmosphere to produce theceramic or ceramic-like silicon nitrogen-containing coating, and (C)applying to the ceramic or ceramic-like coated device a siliconnitrogen-containing coating by means of decomposing in a reactionchamber a silane, halosilane, halodisilane, halopolysilane, or mixturethereof and ammonia, in the vapor phase, at a temperature between 200and 1000 degrees Centigrade, in the presence of the ceramic orceramic-like coated device, whereby an electronic device containing amultilayer, ceramic or ceramic-like, coating thereon is obtained.

The instant invention further relates to a process for forming on asubstrate a multilayer, ceramic or ceramic-like, coating which processcomprises (A) coating an electronic device with a coating by means ofdiluting a hydrolyzed or partially hydrolyzed silicate ester preceramicmaterial with a solvent, coating an electronic device with said dilutedhydrolyzed or partially hydrolyzed silicate ester preceramic materialsolution, drying the diluted hydrolyzed or partially hydrolyzed silicateester preceramic material solution so as to evaporate the solvent andthereby deposit a hydrolyzed or partially hydrolyzed silicate esterpreceramic material coating on the electronic device, ceramifying thehydrolyzed or partially hydrolyzed silicate ester preceramic materialcoating to silicon dioxide by heating the coated device to a temperaturebetween 200 and 1000 degrees Centigrade to produce the ceramic orceramic-like coating, and (B) applying to the ceramic or ceramic-likecoated device a passivating coating which comprises a siliconnitrogen-containing material by means of diluting with a solvent apreceramic silicon nitrogen-containing polymer, coating the ceramic orceramic-like coated device with the diluted preceramic siliconnitrogen-containing polymer solution, drying the diluted preceramicsilicon nitrogen-containing polymer solution so as to evaporate thesolvent and thereby deposit a preceramic silicon nitrogen-containingcoating on the ceramic or ceramic-like coated electronic device, heatingthe coated device to a temperature between 200 and 1000 degreesCentigrade in an inert or ammonia-containing atmosphere to produce theceramic or ceramic-like silicon nitrogen-containing coating, and (C)applying to the ceramic or ceramic-like coated device a siliconcarbon-containing coating by means of decomposing in a reaction chambera silane, alkylsilane, halosilane, halodisilane, halopolysilane, ormixtures thereof, and an alkane of one to six carbon atoms or analkylsilane, in the vapor phase, at a temperature between 200 and 1000degrees Centigrade, in the presence of the ceramic or ceramic-likecoated device, whereby an electronic device containing a multilayer,ceramic or ceramic-like, coating thereon is obtained.

In the instant invention, a hydrolyzed or partially hydrolyzed silicateester preceramic material, for example, ethyl orthosilicate, is diluted(eg., 0.1 to 10 weight %) with a solvent such as isopropyl alcohol orethanol. The diluted preceramic solvent solution is then coated onto anelectronic device and the solvent allowed to evaporate by drying atambient conditions. The process of coating the diluted preceramicpolymer solution onto the electronic device can be, but is not limitedto, spin coating, dip coating, spray coating, or flow coating. Thehydrolyzed or partially hydrolyzed silicate ester preceramic material isoxidized in air, or in water vapor and air, to an SiO₂ -containingmaterial. By this means is deposited a preceramic polymer coating whichis ceramified by heating the coated device, for example, forapproximately one hour at 400 degrees Centigrade. A thin ceramic orceramic-like planarizing coating of less than 2 microns (orapproximately 3000 to 5000 A) is thus produced on the device. Theplanarizing coating thus produced is then coated with a passivatingsilicon nitrogen-containing ceramic or ceramic-like coating of thepresent invention or with a CVD applied silicon-containing coating,silicon carbon-containing coating, or silicon nitrogen-containingcoating or a combination of these coatings.

The second and passivating silicon nitrogen-containing layer of thecomposite coatings in the instant invention provides resistance againstionic impurities. Preceramic SiN-containing polymers suitable for use inthis present invention are well known in the art, including, but notlimited to, silazanes, disilazanes, polysilazanes, cyclic silazanes, andother silicon nitrogen-containing materials. The preceramic siliconnitrogen-containing polymers suitable for use in this invention must becapable of being converted to a ceramic or ceramic-like material atelevated temperatures. Mixtures of preceramic silazane polymers and/orother silicon- and nitrogen-containing materials may also be used inthis invention. Examples of preceramic silazane polymers orpolysilazanes suitable for use in this invention include polysilazanesas described by Gaul in U.S. Pat. Nos. 4,312,970 (issued Jan. 26, 1982),4,340,619 (issued July 20, 1982), 4,395,460 (issued July 26, 1983), and4,404,153 (issued Sept. 13, 1983), all of which are hereby incorporatedby reference. Suitable polysilazanes also include those described byHaluska in U.S. Pat. No. 4,482,689 (issued Nov. 13, 1984) and bySeyferth et al. in U.S. Pat. No. 4,397,828 (issued Aug. 9, 1983), andSeyferth et al. in U.S. Pat. No. 4,482,669 (issued Nov. 13, 1984) whichare hereby incorporated by reference. Other polysilazanes suitable foruse in this invention are disclosed by Cannady in U.S. Pat. Nos.4,540,803 (issued Sept. 10, 1985), 4,535,007 (issued Aug. 13, 1985), and4,543,344 (issued Sept. 24, 1985), and by Baney et al. in U.S. patentapplication Ser. No. 652,939, filed Sept. 21, 1984, all of which arehereby incorporated by reference. Also suitable for use in thisinvention are dihydridosilazane polymers prepared by the reaction of H₂SiX₂, where X=a halogen atom, and NH₃. These (H₂ SiNH)_(n) polymers arewell known in the art, but have not been used for the protection ofelectronic devices. (See, for example, Seyferth, U.S. Pat. No.4,397,828, issued Aug. 9, 1983).

Also to be included as preceramic silicon nitrogen-containing polymermaterials useful within the scope of the present invention are the novelpreceramic polymers derived from the reaction between cyclic silazanesand halogenated disilanes, and also the novel preceramic polymersderived from the reaction between cyclic silazanes and halosilanes.These materials are disclosed and claimed in patent applications of Ser.No. 926,145, titled "Novel Preceramic Polymers Derived From CyclicSilazanes And Halogenated Disilanes And A Method For Their Preparation",and Ser. No. 926,607, titled "Novel Preceramic Polymers Derived FromCyclic Silazanes And Halosilanes And A Method For Their Preparation",respectively, filed in the name of Loren A. Haluska and herebyincorporated by reference. The above-described novel preceramic siliconnitrogen-containing polymers derived from cyclic silazanes andhalosilanes and/or halogenated disilanes are also useful for theprotection of any substrate able to withstand the temperatures necessaryfor ceramification of said preceramic polymers. Still other silicon-andnitrogen-containing materials may be suitable for use in the presentinvention.

In the preparation of the passivating layer of the coatings of theinstant invention, a preceramic polymer containing silicon and nitrogenis diluted to low solids (eg., 0.1 to 10 weight %) in a solvent such astoluene or n-heptane. The diluted silicon nitrogen-containing polymersolvent solution is coated (by any method discussed above) onto theelectronic device previously coated with the ceramified SiO₂ -containingmaterial and the solvent allowed to evaporate by drying in an inert orammonia-containing atmosphere. By this means is deposited a preceramicpolymer coating which is ceramified by heating the coated device forapproximately one hour at temperatures up to 400 degrees Centigradeunder argon. Thin ceramic or ceramic-like passivating coatings of lessthan 2 microns (or approximately 3000 to 5000 A) are thus produced onthe devices.

A preferred temperature range for ceramifying or partially ceramifyingthe silicon nitrogen-containing preceramic polymer is from 200 to 400degrees Centigrade. A more preferred temperature range for ceramifyingthe silicon nitrogen-containing preceramic polymer is from 300 to 400degrees Centigrade. However, the method of applying the heat for theceramification or partial ceramification of the siliconnitrogen-containing coating is not limited to conventional thermalmethods. The silicon nitrogen-containing polymer coatings useful asplanarizing and passivating coatings in the instant invention can alsobe cured by other radiation means, such as, for example, exposure to alaser beam. However, the present invention is not limited toceramification temperatures below 400° Centigrade. Ceramificationtechniques utilizing temperatures up to and including at least 1000°Centigrade will be obvious to those skilled in the art, and are usefulin the present invention where the substrate can withstand suchtemperatures.

By "cure" in the present invention is meant coreaction andceramification or partial ceramification of the starting material byheating to such an extent that a solid polymeric ceramic or ceramic-likecoating material is produced.

Alternatively, in the three layer coating of the instant invention, thesecond and passivating coating can be selected from the group consistingof silicon nitrogen-containing material, silicon carbonnitrogen-containing material, and silicon carbon-containing material.The silicon nitrogen-containing material is deposited by the CVD orplasma enhanced CVD of the reaction product formed by reacting silane,halosilanes, halopolysilanes, or halodisilanes and ammonia. The siliconcarbon-containing material is deposited by the CVD or plasma enhancedCVD of the reaction product formed by reacting silane, alkylsilane,halosilanes, halopolysilanes, or halodisilanes and an alkane of one tosix carbon atoms or an alkylsilane. The silicon carbonnitrogen-containing material is deposited by the CVD or PECVD ofhexamethyldisilazane or by the CVD or PECVD of mixtures comprising asilane, alkylsilane, alkane, and ammonia.

The silicon-containing third layer or topcoat of the composite coatingsof the present invention can be obtained at relatively low reactiontemperature of the metal-assisted CVD process claimed in the parallelU.S. patent application, Ser. No. 835,029, mentioned supra, or byconventional non-metal assisted CVD or plasma enhanced CVD techniques.The metal-assisted CVD process is particularly suited for the depositionof coatings from SiCl₄, SiBr₄, HSiI₃, HSiCl₃, and HSiBr₃.

The choice of substrates and devices to be coated by the instantinvention is limited only by the need for thermal and chemical stabilityof the substrate at the lower decomposition temperature in theatmosphere of the decomposition vessel.

The process of the present invention provides onto the electronicdevices coated with ceramified hydrolyzed or partially hydrolyzedsilicate ester material and ceramified silicon nitrogen-containingmaterial, a silicon-containing topcoating of a thickness which can bevaried as desired depending upon the concentration of the siliconhalides that are being reduced. The top coatings of the instantinvention can be deposited by any known state-of-the-art technique.

Coatings produced by the instant invention possess low defect densityand are useful on electronic devices as protective coatings, ascorrosion resistant and abrasion resistant coatings, as temperature andmoisture resistant coatings, and as a diffusion barrier against ionicimpurities such as Na⁺ and Cl⁻. The silicon nitrogen-containing ceramicor ceramic-like coatings of the instant invention are also useful asinterlevel dielectrics within the body of the electronic device andbetween the metallization layers, thereby replacing spin-on glass films.

The coatings of the present invention are useful for functional purposesin addition to protection of electronic devices from the environment.The coatings of the present invention are also useful as dielectriclayers, doped dielectric layers to produce transistor-like devices,pigment loaded binder systems containing silicon to produce capacitorsand capacitor-like devices, multilayer devices, 3-D devices,silicon-on-insulator (SOI) devices, and super lattice devices.

Another unique aspect of the coatings produced by the present inventionis their transparency to electromagnetic radiation. Thus a particularadvantage of the coatings of the present invention is utilization onfocal plane arrays, photovoltaic cells, or opto-electronic devices inwhich electromagnetic radiation can pass into or emanate from the coateddevice.

EXAMPLE 1

A solution of 8.6 milliliters of ethyl orthosilicate, 8.6 milliliters ofethanol, 2.8 milliliters of water and one drop of 5% hydrochloric acidwas heated at 60 degrees C. for thirty minutes, then was diluted with 60milliliters of ethanol. After standing overnight at room temperature,the solution was flow coated onto aluminum panels, the coating was airdried 10 minutes, and then heat cured in air at 400 degrees for 21/2hours. After cooling to room temperature, the coatings were found to beclear and transparent. Thin ceramic or ceramic-like SiO₂ -containingcoatings of less than 2 microns (or approximately 3000 to 5000 A) werethus produced on the panels.

EXAMPLE 2

An RCA 4011 CMOS electronic device was flow coated with a 1 weightpercent solution of the coating solution of Example 1. The coating wasair dried 10 minutes, then heat cured for 1 hour at 400 degrees C. Bythis process was produced on the electronic device a ceramic orceramic-like SiO₂ -containing planarizing coating of less than 2 microns(or approximately 4000 A).

EXAMPLE 3

A preceramic silazane polymer, prepared by the method of Cannady inExample 1 in U.S. Pat. No. 4,540,803, was diluted to 1.0 weight percentin toluene. The preceramic silazane polymer solvent solution was thenflow coated onto the electronic device coated by the method of example 2and the solvent was allowed to evaporate by drying in the absence ofair. By this means was deposited a preceramic polymer passivatingcoating which was ceramified by heating the coated device forapproximately one hour at 400 degrees Centigrade under argon. Thinsilicon-nitrogen-containing ceramic or ceramic-like passivating coatingsof less than 2 microns (or approximately 3000 Angstroms) were thusproduced on the devices.

EXAMPLE 4

Using the procedure of Example 3, a preceramic silazane polymercontaining about 5 percent titanium, prepared by the method of Haluskain Example 13 in U.S. Pat. No. 4,482,689, was flow coated onto theelectronic device and the solvent allowed to evaporate by drying. Bythis means was deposited a preceramic polymer coating which wasceramified by heating the coated device for approximately one hour attemperatures up to 400 degrees Centigrade under argon. Thin siliconnitrogen-containing ceramic or ceramic-like passivating coatings of lessthan 2 microns (or approximately 3000 Angstroms) were thus produced onthe devices.

EXAMPLE 5

Using the procedure of Example 3, a preceramic silazane polymer,prepared by the method of Gaul in Example 1 in U.S. Pat. No. 4,395,460,was coated onto the electronic device and the solvent allowed toevaporate by drying. By this means was deposited a preceramic polymercoating which was ceramified by heating the coated device forapproximately one hour at temperatures up to 400 degrees Centigradeunder argon. Thin silicon nitrogen-containing ceramic or ceramic-likepassivating coatings of less than 2 microns (or approximately 3000Angstroms) were thus produced on the devices.

EXAMPLE 6

A 1-2 weight % solution in diethyl ether of dihydridosilazane polymer,prepared by the method of Seyferth in Example 1 in U.S. Pat. No.4,397,828, was flow coated onto a CMOS device previously coated by themethod of Example 1, above. The coated device was heated in nitrogen forone hour at 400° C. The coating and pyrolysis treatment did notadversely affect the device function, as determined by a CMOS circuittester. The coated device withstood 0.1M NaCl exposure for over four andone half hours before circuit failure. A nonprotected CMOS device willfail to function after exposure to a 0.1M NaCl solution for less thanone minute.

EXAMPLE 7

The electronic devices coated with the planarizing and/or passivatingcoatings of Examples 1 through 6 were then overcoated with the barriercoats as follows; Hexafluorodisilane, 500 Torr, was placed in a Pyrexglass reaction container along with an electronic device, previouslycoated with a ceramified silicon nitrogen-containing material. Thehexafluorodisilane was transferred to the glass container in such amanner as to preclude exposure to the atmosphere. The reaction containerwas then attached to a vacuum line, the contents evacuated, and thecontainer thoroughly heated under vacuum with a gas-oxygen torch. Thecontainer was sealed with a natural gas-oxygen torch and heated in anoven for 30 minutes at a temperature of approximately 360 degreesCentigrade. During this time the hexafluorodisilane starting materialdecomposed and formed a silicon-containing topcoat on the previouslycoated electronic device. The reaction by-products, mixtures of varioushalosilanes, and any unreacted starting material were removed byevacuation after the container had been reattached to the vacuum line.The ceramic coated electronic device, onto which the decomposedhexafluorodisilane starting material and deposited a silicon-containingtopcoating, was then removed.

EXAMPLE 8

Using the procedure described in Example 7, dichlorodisilane wasthermally decomposed in the presence of the ceramic or ceramic-like SiO₂and silicon nitrogen coated electronic device. An amorphoussilicon-containing topcoat was thereby deposited onto the ceramic orceramic-like coated electronic device. The coated device was tested andall electronic circuits were operable.

That which is claimed is:
 1. A process for forming on an electronicdevice a multilayer, ceramic or ceramic-like coating which processcomprises:(I) (A) coating an electronic device with a planarizingcoating by means of diluting a hydrolyzed or partially hydrolyzedsilicate ester with a solvent and applying the diluted hydrolyzed orpartially hydrolyzed silicate ester solution to an electronic device;(B) drying the hydrolyzed or partially hydrolyzed silicate estersolution so as to evaporate the solvent and thereby deposit a preceramiccoating on the electronic device; (C) ceramifying the hydrolyzed orpartially hydrolyzed silicate ester in air, or in water vapor and air,to silicon dioxide by heating the coated device to a temperature between200 and 1000 degrees Centigrade to produce a ceramic or ceramic-likeplanarizing coating; (II) applying to the ceramic or ceramic-likeplanarizing coating a passivating coating selected from the groupconsisting of (i) a silicon nitrogen-containing coating, (ii) a siliconcarbon-containing coating, and (iii) a silicon carbonnitrogen-containing coating, wherein the silicon nitrogen-containingcoating is applied onto the planarizing coating of the electronic deviceby a means selected from the group consisting of (a) chemical vapordeposition of a silane, halosilane, halodisilane, halopolysilane ormixtures thereof in the presence of ammonia, (b) plasma enhancedchemical vapor deposition of a silane, halosilane, halodisilane,halopolysilane or mixtures thereof in the presence of ammonia, (c)ceramification of a silicon and nitrogen-containing preceramic polymer;and wherein the silicon carbon nitrogen-containing coating is appliedonto the planarizing coating of the electronic device by a meansselected from the group consisting of (1) chemical vapor deposition ofhexamethyldisilazane, (2) plasma enhanced chemical vapor deposition ofhexamethyldisilazane, (3) chemical vapor deposition of a silane,alkylsilane, halosilane, halodisilane, halopolysilane or mixture thereofin the presence of an alkane of one to six carbon atoms or analkylsilane and further in the presence of ammonia, and (4) plasmaenhanced chemical vapor deposition of a silane, alkylsilane, halosilane,halodisilane, halopolysilane or mixture thereof in the presence of analkane of one to six carbon atoms or an alkylsilane and further in thepresence of ammonia; and wherein the silicon carbon-containing coatingis deposited by a means selected from the group consisting of (i)chemical vapor deposition of a silane, alkylsilane, halosilane,halodisilane, halopolysilane or mixtures thereof in the presence of analkane of one to six carbon atoms or an alkylsilane, and (ii) plasmaenhanced chemical vapor deposition of a silane, alkylsilane, halosilane,halodisilane, halopolysilane or mixtures thereof in the presence of analkane of one to six carbon atoms or an alkylsilane, to produce thepassivating ceramic or ceramic-like coating, and (III) applying to thepassivating ceramic or ceramic-like coating a silicon-containing coatingselected from the group consisting of (i) silicon coating, (ii) siliconcarbon-containing coating, (iii) silicon nitrogen-containing coating,and (iv) silicon carbon nitrogen-containing coating, wherein the siliconcoating is applied onto the passivating coating by a means selected fromthe group consisting of (a) chemical vapor deposition of a silane,halosilane, halodisilane, halopolysilane or mixtures thereof, (b) plasmaenhanced chemical vapor deposition of a silane, halosilane,halodisilane, halopolysilane or mixtures thereof, or (c) metal assistedchemical vapor deposition of a silane, halosilane, halodisilane,halopolysilane or mixtures thereof, and wherein the siliconcarbon-containing coating is applied by a means selected from the groupconsisting of (1) chemical vapor deposition of a silane, alkylsilane,halosilane, halodisilane, halopolysilane or mixtures thereof in thepresence of an alkane of one to six carbon atoms or an alkylsilane, (2)plasma enhanced chemical vapor deposition of a silane, alkylsilane,halosilane, halodisilane, halopolysilane or mixtures thereof in thepresence of an alkane of one to six carbon atoms or an alkylsilane; andwherein the silicon nitrogen-containing coating is deposited by a meansselected from the group consisting of (A) chemical vapor deposition of asilane, halosilane, halodisilane, halopolysilane or mixtures thereof inthe presence of ammonia, (B) plasma enhanced chemical vapor depositionof a silane, halosilane, halodisilane, halopolysilane or mixturesthereof in the presence of ammonia, and (C) ceramification of a siliconand nitrogen-containing preceramic polymer, and wherein the siliconcarbon nitrogen-containing coating is deposited by a means selected fromthe group consisting of (i) chemical vapor deposition ofhexamethyldisilazane, (ii) plasma enhanced chemical vapor deposition ofhexamethyldisilazine, (iii) chemical vapor deposition of a silane,alkylsilane, halosilane, halodisilane, halopolysilane or mixture thereofin the presence of an alkane of one to six carbon atoms or analkylsilane and further in the presence of ammonia, and (iv) plasmaenhanced chemical vapor deposition of a silane, alkylsilane, halosilane,halodisilane, halopolysilane or mixture thereof in the presence of analkane of one to six carbon atoms or an alkylsilane and further in thepresence of ammonia, to produce the silicon-containing coating, wherebya multilayer, ceramic or ceramic-like, coating is obtained on theelectronic device.
 2. An article comprising a structure having thereon acoating prepared by the process of claim
 1. 3. An electronic devicecoated by the process of claim
 1. 4. An electronic device comprising astructure having therein a coating prepared by the process of claim 1wherein the coating is used as an interlevel dielectric layer.
 5. Aprocess as claimed in claim 1 wherein the coating technique used todeposit the hydrolyzed or partially hydrolyzed silicate ester preceramicmaterial solution onto the electronic device is selected from the groupconsisting of spray coating, dip coating, flow coating and spin coating.6. A process as claimed in claim 1 wherein the coated device is heatedto a temperature in the range of 200 to 400 degrees Centigrade toproduce the ceramic or ceramic-like planarizing coating.
 7. A processfor forming on an electronic device a dual layer, ceramic orceramic-like coating which process comprises:(I) (A) coating anelectronic device with a planarizing coating by means of diluting ahydrolyzed or partially hydrolyzed silicate ester with a solvent andapplying the diluted hydrolyzed or partially hydrolyzed silicate estersolution to an electronic device; (B) drying the diluted hydrolyzed orpartially hydrolyzed silicate ester solution so as to evaporate thesolvent and thereby deposit a preceramic coating on the electronicdevice; (C) ceramifying the hydrolyzed or partially hydrolyzed silicateester in air, or in water vapor and air, to silicon dioxide by heatingthe coated device to a temperature between 200 and 1000 degreesCentigrade to produce a ceramic or ceramic-like planarizing coating; and(II) applying to the ceramic or ceramic-like planarizing coating apassivating coating selected from the group consisting of (i) asilicon-containing coating, (ii) a silicon nitrogen-containing coating,(iii) a silicon carbon-containing coating, and (iv) a silicon carbonnitrogen-containing coating, wherein the silicon-containing coating isapplied onto the planarizing coating of the electronic device by a meansselected from the group consisting of (a) chemical vapor deposition of asilane, halosilane, halodisilane, halopolysilane or mixtures thereof,(b) plasma enhanced chemical vapor deposition of a silane, halosilane,halodisilane, halopolysilane or mixtures thereof, or (c) metal assistedchemical vapor deposition of a silane, halosilane, halodisilane,halopolysilane or mixtures thereof; wherein the siliconnitrogen-containing coating is applied onto the ceramic or ceramic-likecoated electronic device by a means selected from the group consistingof (a) chemical vapor deposition of a silane, halosilane, halodisilane,halopolysilane or mixtures thereof in the presence of ammonia, (b)plasma enhanced chemical vapor deposition of a silane, halosilane,halodisilane, halopolysilane or mixtures thereof in the presence ofammonia, (c) ceramification of a silicon and nitrogen-containingpreceramic polymer; and wherein the silicon carbon nitrogen-containingcoating is applied onto the planarizing coating of the electronic deviceby a means selected from the group consisting of (1) chemical vapordeposition of hexamethyldisilazane, (2) plasma enhanced chemical vapordeposition of hexamethyldisilazane, (3) chemical vapor deposition of asilane, alkylsilane, halosilane, halodisilane, halopolysilane or mixturethereof in the presence of an alkane of one to six carbon atoms or analkylsilane and further in the presence of ammonia, and (4) plasmaenhanced chemical vapor deposition of a silane, alkylsilane, halosilane,halodisilane, halopolysilane or mixture thereof in the presence of analkane of one to six carbon atoms or an alkylsilane and further in thepresence of ammonia; and wherein the silicon carbon-containing coatingis deposited by a means selected from the group consisting of (i)chemical vapor deposition of a silane, alkylsilane, halosilane,halodisilane, halopolysilane or mixtures thereof in the presence of analkane of one to six carbon atoms or an alkylsilane, and (ii) plasmaenhanced chemical vapor deposition of a silane, alkylsilane, halosilane,halodisilane, halopolysilane or mixtures thereof in the presence of analkane of one to six carbon atoms or an alkylsilane, to produce thepassivating ceramic or ceramic-like coating, whereby a dual layer,ceramic or ceramic-like coating is obtained on the electronic device. 8.An article comprising a structure having thereon a coating prepared bythe process of claim
 7. 9. An electronic device coated by the process ofclaim
 7. 10. A process for forming on an electronic device a multilayer,ceramic or ceramic-like coating which process comprises:(A) coating anelectronic device with a coating by means of diluting a hydrolyzed orpartially hydrolyzed silicate ester preceramic material with a solvent,coating an electronic device with said diluted preceramic hydrolyzed orpartially hydrolyzed silicate ester solution, drying the dilutedpreceramic hydrolyzed or partially hydrolyzed silicate ester solution soas to evaporate the solvent and thereby deposit a preceramic coating onthe electronic device, ceramifying the hydrolyzed or partiallyhydrolyzed silicate ester in air, or in water vapor and air, to silicondioxide by heating the coated device at a temperature of 200 to 1000degrees Centigrade to produce a ceramic or ceramic-like coating, and (B)applying to the ceramic or ceramic-like coated device asilicon-containing coating by means of decomposing in a reaction chambera silane halosilane, halodisilane, halopolysilane, or mixture thereof inthe vapor phase, at a temperature between 200 and 600 degreesCentigrade, in the presence of the ceramic coated device, whereby anelectronic device containing a multilayer, ceramic or ceramic-likecoating thereon is obtained.
 11. A process as claimed in claim 10wherein the silicon-containing coating is applied by means of plasmaenhanced chemical vapor deposition.
 12. An article comprising astructure having thereon a coating prepared by the process of claim 11.13. An electronic device coated by the process of claim
 11. 14. Aprocess as claimed in claim 10 wherein the silicon-containing coating isapplied by means of metal assisted chemical vapor deposition.
 15. Anarticle comprising a structure having thereon a coating prepared by theprocess of claim
 14. 16. An electronic device coated by the process ofclaim
 14. 17. An article comprising a structure having thereon a coatingprepared by the process of claim
 10. 18. An electronic device coated bythe process of claim
 10. 19. A process for forming on an electronicdevice a multilayer, ceramic or ceramic-like coating which processcomprises:(A) coating an electronic device with a coating by means ofdiluting a hydrolyzed or partially hydrolyzed silicate ester preceramicmaterial with a solvent, coating an electronic device with said dilutedpreceramic hydrolyzed or partially hydrolyzed silicate ester solution,drying the diluted preceramic hydrolyzed or partially hydrolyzedsilicate ester solution so as to evaporate the solvent and therebydeposit a preceramic coating on the electronic device, ceramifying thehydrolyzed or partially hydrolyzed silicate ester in air, or in watervapor and air, to silicon dioxide by heating the coated device attemperatures of 200 to 1000 degrees Centigrade to produce the ceramic orceramic-like coating, and, (B) applying to the ceramic or ceramic-likecoated device a silicon nitrogen-containing coating by means ofdecomposing in a reaction chamber a silane, halosilane, halodisilane,halopolysilane, or mixture thereof, and ammonia, in the vapor phase, ata temperature between 200 and 1000 degrees Centigrade, in the presenceof the ceramic or ceramic-like coated device, whereby an electronicdevice containing a multilayer, ceramic or ceramic-like coating thereonis obtained.
 20. A process as claimed in claim 19 wherein the siliconnitrogen-containing coating is applied by means of plasma enhancedchemical vapor deposition.
 21. An article comprising a structure havingthereon a coating prepared by the process of claim
 20. 22. An electronicdevice coated by the process of claim
 20. 23. A process as claimed inclaim 19 wherein the silicon nitrogen-containing coating is applied bymeans of metal assisted chemical vapor deposition.
 24. An articlecomprising a structure having thereon a coating prepared by the processof claim
 23. 25. An electronic device coated by the process of claim 23.26. An article comprising a structure having thereon a coating preparedby the process of claim
 19. 27. An electronic device coated by theprocess of claim
 19. 28. A process for forming on an electronic device amultilayer, ceramic or ceramic-like coating which process comprises:(A)coating an electronic device with a coating by means of diluting ahydrolyzed or partially hydrolyzed silicate ester preceramic materialwith a solvent, coating an electronic device with said dilutedpreceramic hydrolyzed or partially hydrolyzed silicate ester solution,drying the diluted preceramic hydrolyzed or partially hydrolyzedsilicate ester solution so as to evaporate the solvent and therebydeposit a preceramic coating on the electronic device, ceramifying thehydrolyzed or partially hydrolyzed silicate ester in air, or in watervapor and air, to silicon dioxide by heating the coated device attemperatures of 200 to 1000 degrees Centigrade to produce the ceramic orceramic-like coating, and, (B) applying to the ceramic or ceramic-likecoated device a silicon carbon-containing coating by means ofdecomposing in a reaction chamber a silane, alkylsilane, halosilane,halodisilane, halopolysilane, or mixture thereof, and an alkane of oneto six carbon atoms or an alkylsilane, in the vapor phase, at atemperature between 200 and 1000 degrees Centigrade, in the presence ofthe ceramic or ceramic-like coated device, whereby an electronic devicecontaining a multilayer, ceramic or ceramic-like coating thereon isobtained.
 29. A process as claimed in claim 28 wherein the siliconcarbon-containing coating is applied by means of plasma enhancedchemical vapor deposition.
 30. An article comprising a structure havingthereon a coating prepared by the process of claim
 29. 31. An electronicdevice coated by the process of claim
 29. 32. A process as claimed inclaim 28 wherein the silicon carbon-containing coating is applied bymeans of metal assisted chemical vapor deposition.
 33. An articlecomprising a structure having thereon a coating prepared by the processof claim
 32. 34. An electronic device coated by the process of claim 32.35. An article comprising a structure having thereon a coating preparedby the process of claim
 28. 36. An electronic device coated by theprocess of claim
 28. 37. A process for forming on an electronic device amultilayer, ceramic or ceramic-like coating which process comprises:(A)coating an electronic device with a coating by means of diluting ahydrolyzed or partially hydrolyzed silicate ester preceramic materialwith a solvent, coating an electronic device with said dilutedpreceramic hydrolyzed or partially hydrolyzed silicate ester solution,drying the diluted preceramic hydrolyzed or partially hydrolyzedsilicate ester solution so as to evaporate the solvent and therebydeposit a preceramic coating on the electronic device, ceramifying thehydrolyzed or partially hydrolyzed silicate ester in air, or in watervapor and air, to silicon dioxide by heating the coated device attemperatures of 200 to 1000 degrees Centigrade to produce a ceramic orceramic-like coating, and, (B) applying to the ceramic or ceramic-likecoated device a silicon carbon nitrogen-containing coating by means ofdecomposing in a reaction chamber hexamethyldisilazane, in the vaporphase, at a temperature between 200 and 1000 degrees Centigrade, in thepresence of the ceramic or ceramic-like coated device, whereby anelectronic device containing a multilayer, ceramic or ceramic-likecoating thereon is obtained.
 38. A process as claimed in claim 37wherein the silicon carbon nitrogen-containing coating is applied bymeans of plasma enhanced chemical vapor deposition.
 39. An articlecomprising a structure having thereon a coating prepared by the processof claim
 38. 40. An electronic device coated by the process of claim 38.41. A process as claimed in claim 37 wherein the silicon carbonnitrogen-containing coating is applied by means of metal assistedchemical vapor deposition.
 42. An article comprising a structure havingthereon a coating prepared by the process of claim
 41. 43. An electronicdevice coated by the process of claim
 4. 44. An article comprising astructure having thereon a coating prepared by the process of claim 37.45. An electronic device coated by the process of claim
 37. 46. Aprocess for forming on an electronic device a multilayer, ceramic orceramic-like coating which process comprises:(A) coating an electronicdevice with a coating by means of diluting a hydrolyzed or partiallyhydrolyzed silicate ester preceramic material with a solvent, coating anelectronic device with said diluted preceramic hydrolyzed or partiallyhydrolyzed silicate ester solution, drying the diluted preceramichydrolyzed or partially hydrolyzed silicate ester solution so as toevaporate the solvent and thereby deposit a preceramic coating on theelectronic device, ceramifying the hydrolyzed or partially hydrolyzedsilicate ester in air, or in water vapor and air, to silicon dioxide byheating the coated device at temperatures of 200 to 1000 degreesCentigrade to produce the ceramic or ceramic-like coating, and, (B)applying to the ceramic or ceramic-like coated device a silicon carbonnitrogen-containing coating by means of chemical vapor deposition of asilane, alkylsilane, halosilane, halodisilane, halopolysilane or mixturethereof in the presence of an alkane of one to six carbon atoms or analkylsilane and further in the presence of ammonia, to produce thesilicon-containing coating, whereby a multilayer, ceramic orceramic-like, coating is obtained on the electronic device.
 47. Anarticle comprising a structure having thereon a coating prepared by theprocess of claim
 46. 48. An electronic device coated by the process ofclaim
 46. 49. A process for forming on an electronic device amultilayer, ceramic or ceramic-like coating which process comprises:(A)coating an electronic device with a coating by means of diluting ahydrolyzed or partially hydrolyzed silicate ester preceramic materialwith a solvent, coating an electronic device with said dilutedpreceramic hydrolyzed or partially hydrolyzed silicate ester solution,drying the diluted preceramic hydrolyzed or partially hydrolyzedsilicate ester solution so as to evaporate the solvent and therebydeposit a preceramic coating on the electronic device, ceramifying thehydrolyzed or partially hydrolyzed silicate ester in air, or in watervapor and air, to silicon dioxide by heating the coated device attemperatures of 200 to 1000 degrees Centigrade to produce the ceramic orceramic-like coating, and, (B) applying to the ceramic or ceramic-likecoated device a silicon carbon nitrogen-containing coating by means ofplasma enhanced chemical vapor deposition of a silane, alkylsilane,halosilane, halodisilane, halopolysilane or mixture thereof in thepresence of an alkane of one to six carbon atoms or an alkylsilane andfurther in the presence of ammonia, to produce the silicon-containingcoating, whereby a multilayer, ceramic or ceramic-like, coating isobtained on the electronic device.
 50. An article comprising a structurehaving thereon a coating prepared by the process of claim
 49. 51. Anelectronic device coated by the process of claim
 49. 52. A process forforming on an electronic device a multilayer, ceramic or ceramic-likecoating which process comprises:(A) coating an electronic device with acoating by means of diluting a hydrolyzed or partially hydrolyzedsilicate ester preceramic material with a solvent, coating an electronicdevice with the diluted preceramic hydrolyzed or partially hydrolyzedsilicate ester solution, drying the diluted preceramic hydrolyzed orpartially hydrolyzed silicate ester solution so as to evaporate thesolvent and thereby deposit a preceramic coating on the electronicdevice, ceramifying the hydrolyzed or partially hydrolyzed silicateester in air, or in water vapor and air, to silicon dioxide by heatingthe coated device to a temperature between 200 and 1000 degreesCentigrade to produce a ceramic or ceramic-like coating, and, (B)applying to the ceramic or ceramic-like coated device a passivatingcoating comprising a silicon nitrogen-containing material produced bymeans of diluting in a solvent a preceramic silicon nitrogen-containingpolymer, coating the ceramic or ceramic-like coated device with thediluted preceramic silicon nitrogen-containing polymer solution, dryingthe diluted preceramic silicon nitrogen-containing polymer solution soas to evaporate the solvent and thereby deposit a preceramic siliconnitrogen-containing coating on the ceramic or ceramic-like coatedelectronic device, heating the coated device to a temperature of 200 to1000 degrees Centigrade in an inert or ammonia-containing atmosphere toproduce the ceramic silicon nitrogen-containing coating, and (C)applying to the ceramic coated device a silicon-containing coating bymeans of decomposing in a reaction chamber a silane, halosilane,halodisilane or mixture thereof in the vapor phase, at a temperaturebetween 200 and 600 degrees Centigrade, in the presence of the ceramicor ceramic-like coated device, whereby an electronic device containing amultilayer, ceramic or ceramic-like coating thereon is obtained.
 53. Anarticle comprising a structure having thereon a coating prepared by theprocess of claim
 52. 54. An electronic device coated by the process ofclaim
 52. 55. A process as claimed in claim 52 wherein the coatingtechnique used to deposit the preceramic silicon nitrogen-containingpolymer solution onto the electronic device is selected from the groupconsisting of spray coating, dip coating, flow coating and spin coating.56. A process for forming on an electronic device a multilayer, ceramicor ceramic-like coating which process comprises:(A) coating anelectronic device with a ceramic or ceramic-like coating by means ofdiluting a hydrolyzed or partially hydrolyzed silicate ester preceramicmaterial with a solvent, coating an electronic device with saidpreceramic hydrolyzed or partially hydrolyzed silicate ester solution,drying the preceramic hydrolyzed or partially hydrolyzed silicate estersolution so as to evaporate the solvent and thereby deposit a preceramiccoating on the electronic device, ceramifying the hydrolyzed orpartially hydrolyzed silicate ester in air or in water vapor and air tosilicon dioxide by heating the coated device to a temperature between200 and 1000 degrees Centigrade to produce the ceramic or ceramic-likecoating, and, (B) applying to the ceramic or ceramic-like coated devicea passivating coating comprising a silicon nitrogen-containing materialproduced by means of diluting in a solvent a preceramic siliconnitrogen-containing polymer, coating the ceramic ceramic-like coateddevice with the diluted preceramic silicon nitrogen-containing polymersolution, drying the diluted preceramic silicon nitrogen-containingpolymer solution so as to evaporate the solvent and thereby deposit apreceramic silicon nitrogen-containing coating on the ceramic orceramic-like coated electronic device, heating the coated device to atemperature between 200 and 100 degrees Centigrade in an inert orammonia-containing atmosphere to produce the ceramic siliconnitrogen-containing coating, and (C) applying to the ceramic orceramic-like coated device a silicon nitrogen-containing coating bymeans of decomposing in a reaction chamber a silane, halosilane,halodisilane, halopolysilane or mixture thereof, and ammonia, in thevapor phase, at a temperature between 200 and 1000 degrees Centigrade,in the presence of the ceramic or ceramic-like coated device, whereby anelectronic device containing a multilayer, ceramic or ceramic-likecoating thereon is obtained.
 57. An article comprising a structurehaving thereon a coating prepared by the process of claim
 56. 58. Anelectronic device coated by the process of claim
 56. 59. A process forforming on an electronic device a multilayer, ceramic or ceramic-likecoating which process comprises:(A) coating an electronic device with acoating by means of diluting a hydrolyzed or partially hydrolyzedsilicate ester preceramic material with a solvent, coating an electronicdevice with said diluted preceramic hydrolyzed or partially hydrolyzedsilicate ester solution, drying the diluted preceramic hydrolyzed orpartially hydrolyzed silicate ester solution so as to evaporate thesolvent and thereby deposit a preceramic coating on the electronicdevice, ceramifying the hydrolyzed or partially hydrolyzed silicateester in air, or in water vapor and air, to silicon dioxide by heatingthe coated device to a temperature between 200 and 1000 degreesCentigrade to produce the ceramic or ceramic-like coating, and, (B)applying to the ceramic or ceramic-like coated device a passivatingcoating comprising a silicon nitrogen-containing material produced bymeans of diluting in a solvent a preceramic silicon nitrogen-containingpolymer, coating the ceramic or ceramic-like coated device with thediluted preceramic silicon nitrogen-containing polymer solution, dryingthe diluted preceramic silicon nitrogen-containing polymer solution soas to evaporate the solvent and thereby deposit a preceramic siliconnitrogen-containing coating on the ceramic or ceramic-like coatedelectronic device, heating the coated device to a temperature between200 and 100 degrees Centigrade in an inert or ammonia-containingatmosphere to produce the ceramic or ceramic-like siliconnitrogen-containing coating, and (C) applying to the ceramic orceramic-like coated device a silicon carbon-containing coating by meansof decomposing in a reaction chamber a silane, alkylsilane, halosilane,halodisilane, halopolysilane or mixture thereof, and an alkane of one tosix carbon atoms or an alkylsilane, in the vapor phase, at a temperaturebetween 200 and 1000 degrees Centigrade, in the presence of the ceramicor ceramic coated device, whereby an electronic device containing amultilayer, ceramic or ceramic-like coating thereon is obtained.
 60. Anarticle comprising a structure having thereon a coating prepared by theprocess of claim
 59. 61. An electronic device coated by the process ofclaim
 59. 62. A process for forming on an electronic device amultilayer, ceramic or ceramic-like coating which process comprises:(A)coating an electronic device with a coating by means of diluting ahydrolyzed or partially hydrolyzed silicate ester preceramic materialwith a solvent, coating an electronic device with said dilutedpreceramic hydrolyzed or partially hydrolyzed silicate ester solution,drying the diluted preceramic hydrolyzed or partially hydrolyzedsilicate ester solution so as to evaporate the solvent and therebydeposit a preceramic coating on the electronic device, ceramifying thehydrolyzed or partially hydrolyzed silicate ester in air, or in watervapor and air, to silicon dioxide by heating the coated device attemperatures of 200 to 1000 degrees Centigrade to produce the ceramic orceramic-like coating, and, (B) applying to the ceramic or ceramic-likecoated device a passivating coating comprising a siliconnitrogen-containing material produced by means of diluting in a solventa preceramic silicon nitrogen-containing polymer, coating the ceramic orceramic-like coated device with the diluted preceramic siliconnitrogen-containing polymer solution, drying the diluted preceramicsilicon nitrogen-containing polymer solution so as to evaporate thesolvent and thereby deposit a preceramic silicon nitrogen-containingcoating on the ceramic or ceramic-like coated electronic device, heatingthe coated device to a temperature between 200 and 1000 degreesCentigrade in an inert or ammonia-containing atmosphere to produce theceramic or ceramic-like silicon nitrogen-containing coating, and, (C)applying to the ceramic or ceramic-like coated device a silicon carbonnitrogen-containing coating by means of chemical vapor deposition ofhexamethyldisilazane, in the presence of the ceramic or ceramic-likecoated device, whereby an electronic device containing a multilayer,ceramic or ceramic-like coating thereon is obtained.
 63. An articlecomprising a structure having thereon a coating prepared by the processof claim
 62. 64. An electronic device coated by the process of claim 62.65. A process for forming on an electronic device a multilayer, ceramicor ceramic-like coating which process comprises:(A) coating anelectronic device with a coating by means of diluting a hydrolyzed orpartially hydrolyzed silicate ester preceramic material with a solvent,coating an electronic device with said diluted preceramic hydrolyzed orpartially hydrolyzed silicate ester solution, drying the dilutedpreceramic hydrolyzed or partially hydrolyzed silicate ester solution soas to evaporate the solvent and thereby deposit a preceramic coating onthe electronic device, ceramifying the hydrolyzed or partiallyhydrolyzed silicate ester in air, or in water vapor and air, to silicondioxide by heating the coated device at temperatures of 200 to 1000degrees Centigrade to produce the ceramic or ceramic-like coating, and,(B) applying to the ceramic or ceramic-like coating a passivatingcoating comprising a silicon nitrogen-containing material produced bymeans of diluting in a solvent a preceramic silicon nitrogen-containingpolymer, coating the ceramic or ceramic-like coated device with thediluted preceramic silicon nitrogen-containing polymer solution, dryingthe diluted preceramic silicon nitrogen-containing polymer solution soas to evaporate the solvent and thereby deposit a preceramic siliconnitrogen-containing coating on the ceramic or ceramic-like coatedelectronic device, heating the coated device to a temperature between200 and 1000 degrees Centigrade in an inert or ammonia-containingatmosphere to produce the ceramic or ceramic-like siliconnitrogen-containing coating, and, (C) applying to the ceramic orceramic-like coating a silicon carbon nitrogen-containing coating bymeans of plasma enhanced chemical vapor deposition ofhexamethyldisilazane, in the presence of the ceramic or ceramic-likecoated device, whereby an electronic device containing a multilayer,ceramic or ceramic-like coating thereon is obtained.
 66. An articlecomprising a structure having thereon a coating prepared by the processof claim
 65. 67. An electronic device coated by the process of claim 65.68. A process for forming on an electronic device a multilayer, ceramicor ceramic-like coating which process comprises:(A) coating anelectronic device with a coating by means of diluting a hydrolyzed orpartially hydrolyzed silicate ester preceramic material with a solvent,coating an electronic device with said diluted preceramic hydrolyzed orpartially hydrolyzed silicate ester solution, drying the dilutedpreceramic hydrolyzed or partially hydrolyzed silicate ester solution soas to evaporate the solvent and thereby deposit a preceramic coating onthe electronic device, ceramifying the hydrolyzed or partiallyhydrolyzed silicate ester in air, or in water vapor and air, to silicondioxide by heating the coated device at temperatures of 200 to 1000degrees Centigrade to produce the ceramic or ceramic-like coating, and,(B) applying to the ceramic or ceramic-like coated device a passivatingcoating comprising a silicon nitrogen-containing material produced bymeans of diluting in a solvent a preceramic silicon nitrogen-containingpolymer, coating the ceramic or ceramic-like coated device with thediluted preceramic silicon nitrogen-containing polymer solution, dryingthe diluted preceramic silicon nitrogen-containing polymer solution soas to evaporate the solvent and thereby deposit a preceramic siliconnitrogen-containing coating on the ceramic or ceramic-like coatedelectronic device, heating the coated device to a temperature between200 and 1000 degrees Centigrade in an inert or ammonia-containingatmosphere to produce the ceramic or ceramic-like siliconnitrogen-containing coating, and, (C) applying to the ceramic orceramic-like coated device a silicon carbon nitrogen-containing coatingby means of chemical vapor deposition of a silane, alkylsilane,halosilane, halodisilane, halopolysilane or mixture thereof in thepresence of an alkane of one to six carbon atoms or an alkylsilane andfurther in the presence of ammonia, to produce the silicon carbonnitrogen-containing coating, whereby a multilayer, ceramic orceramic-like, coating is obtained on the electronic device.
 69. Anarticle comprising a structure having thereon a coating prepared by theprocess of claim
 68. 70. An electronic device coated by the process ofclaim
 68. 71. A process for forming on an electronic device amultilayer, ceramic or ceramic-like coating which process comprises:(A)coating an electronic device with a coating by means of diluting ahydrolyzed or partially hydrolyzed silicate ester preceramic materialwith a solvent, coating an electronic device with said dilutedpreceramic hydrolyzed or partially hydrolyzed silicate ester solution,drying the diluted preceramic hydrolyzed or partially hydrolyzedsilicate ester solution so as to evaporate the solvent and therebydeposit a preceramic coating on the electronic device, ceramifying thehydrolyzed or partially hydrolyzed silicate ester in air, or in watervapor and air, to silicon dioxide by heating the coated device attemperatures of 200 to 1000 degrees Centigrade to produce a ceramic orceramic-like coating, and, (B) applying to the ceramic or ceramic-likecoated device a passivating coating comprising a siliconnitrogen-containing material produced by means of diluting in a solventa preceramic silicon nitrogen-containing polymer, coating the ceramic orceramic-like coated device with the diluted preceramic siliconnitrogen-containing polymer solution, drying the diluted preceramicsilicon nitrogen-containing polymer solution so as to evaporate thesolvent and thereby deposit a preceramic silicon nitrogen-containingcoating on the ceramic or ceramic-like coated electronic device, heatingthe coated device to a temperature between 200 and 1000 degreesCentigrade in an inert or ammonia-containing atmosphere to produce theceramic or ceramic-like silicon nitrogen-containing coating, and, (C)applying to the ceramic or ceramic-like coated device a silicon carbonnitrogen-containing coating by means of plasma enhanced chemical vapordeposition of a silane, alkylsilane, halosilane, halodisilane,halopolysilane or mixture thereof in the presence of an alkane of one tosix carbon atoms or an alkylsilane and further in the presence ofammonia, to produce the silicon-containing coating, whereby amultilayer, ceramic or ceramic-like, coating is obtained on theelectronic device.
 72. An article comprising a structure having thereona coating prepared by the process of claim
 71. 73. An electronic devicecoated by the process of claim
 71. 74. A process for forming on anelectronic device a dual layer, ceramic or ceramic-like coating whichprocess comprises:(A) coating an electronic device with a coating bymeans of diluting a hydrolyzed or partially hydrolyzed silicate esterpreceramic material with a solvent, coating an electronic device withsaid diluted preceramic hydrolyzed or partially hydrolyzed silicateester solution, drying the diluted preceramic hydrolyzed or partiallyhydrolyzed silicate ester solution so as to evaporate the solvent andthereby deposit a preceramic coating on the electronic device,ceramifying the hydrolyzed or partially hydrolyzed silicate ester inair, or in water vapor and air, to silicon dioxide by heating the coateddevice to a temperature between 200 and 1000 degrees Centigrade toproduce the ceramic or ceramic-like coating, and, (B) applying to theceramic or ceramic-like coated device a passivating coating comprising asilicon nitrogen-containing material produced by means of diluting in asolvent a preceramic silicon nitrogen-containing polymer, coating theceramic or ceramic-like coated device with the preceramic siliconnitrogen-containing polymer solution, drying the preceramic siliconnitrogen-containing polymer solution so as to evaporate the solvent andthereby deposit a preceramic silicon nitrogen-containing coating on theceramic or ceramic-like coated electronic device, and heating the coateddevice to a temperature between 200 and 1000 degrees Centigrade in aninert or ammonia-containing atmosphere to produce the passivatingsilicon nitrogen-containing coating, thereby producing a dual layer,ceramic or ceramic-like coating on the electronic device.
 75. A methodof coating a substrate with a ceramic or ceramic-like siliconnitrogen-containing material, wherein said method comprises the stepsof:(1) diluting with a solvent a silicon and nitrogen-containingpreceramic polymer produced by reacting a cyclic silazane or a mixtureof cyclic silazanes with a silicon-containing material selected from thegroup consisting of halodisilanes and halosilanes; (2) coating asubstrate with the diluted preceramic polymer solvent solution; (3)drying the diluted polymer solvent solution in the absence of air so asto evaporate the solvent and thereby deposit a preceramic polymercoating on the substrate; and (4) heating the coated substrate in theabsence of air to produce a ceramic or ceramic-like coated substrate.76. A method as claimed in claim 75 wherein the substrate is the surfaceof an electronic device.